A series of new macrobicyclic tetrathiafulvalenophanes of type 1 and 2 with three tetrathiafulvalene bridges has been prepared under high‐dilution conditions using a stepwise selective protection‐deprotection of tetrathiafulvalenethiolates. All the macrobicyclic tetrathiafulvalenes, along with the intermediate compounds 5 and 6 and the unexpected tetrathiafulvalene pentamers 17, were studied by cyclic voltammetry. An electrochemical investigation using the Bard‐Anson equation and thin‐layer cyclic voltammetry has been carried out, allowing an estimate of the number of electrons involved in each redox process of these multi‐redox compounds. The X‐ray crystal structure showing the unusual crystal packing of 2a is also presented.